Dr. Mohamed E. I.

Badawy Analytical Chemistry

Redox Titration Curves

To evaluate a redox titration we must know the shape of its titration curve. In an
acid–base titration or a complexation titration, a titration curve shows the change in
concentration of H3O+ (as pH) or Mn+ (as pM) as a function of the volume of titrant.
For a redox titration, it is convenient to monitor electrochemical potential. You will
recall that the Nernst equation relates the electrochemical potential to the
concentrations of reactants and products participating in a redox reaction. Consider,
for example, a titration in which the analyte in a reduced state, Ared, is titrated with a
titrant in an oxidized state, Tox. The titration reaction is
Ared + Tox → Tred + Aox
The electrochemical potential for the reaction is the difference between the reduction
potentials for the reduction and oxidation half-reactions; thus,
Erxn = ETox/Tred – EAox/Ared
After each addition of titrant, the reaction between the analyte and titrant reaches a
state of equilibrium. The reaction’s electrochemical potential, Erxn, therefore, is zero,
and
ETox/Tred = EAox /Ared
Consequently, the potential for either half-reaction may be used to monitor the
titration’s progress. Before the equivalence point the titration mixture consists of
appreciable quantities of both the oxidized and reduced forms of the analyte, but very
little unreacted titrant. The potential, therefore, is best calculated using the Nernst
equation for the analyte’s half-reaction

Although E°Aox /Ared is the standard-state potential for the analyte’s half-reaction, a
matrix-dependent formal potential is used in its place. After the equivalence point,
the potential is easiest to calculate using the Nernst equation for the titrant’s half-
reaction, since significant quantities of its oxidized and reduced forms are present.

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Dr. Mohamed E. I. Badawy Analytical Chemistry

Formal potential: The potential of a redox reaction for a specific set of solution
conditions, such as pH and ionic composition.
Calculating the Titration Curve:
As an example, let’s calculate the titration curve for the titration of 50.0 mL of
0.100 M Fe2+ with 0.100 M Ce4+ in a matrix of 1 M HClO4. The reaction in this case
is:
Fe2+(aq) + Ce4+(aq) → Ce3+(aq) + Fe3+(aq)
The equilibrium constant for this reaction is quite large (it is approximately 6 ×1015),
so we may assume that the analyte and titrant react completely.
The first task is to calculate the volume of Ce4+ needed to reach the equivalence point.
From the stoichiometry of the reaction we know Moles Fe2+ = moles Ce4+ or:
MFeVFe = MCeVCe
Solving for the volume of Ce4+

Gives the equivalence point volume as 50.0 mL.

Before the equivalence point the concentration of unreacted Fe2+ and the
concentration of Fe3+ produced by the reaction are easy to calculate. For this reason
we find the potential using the Nernst equation for the analyte’s half-reaction

The concentrations of Fe2+ and Fe3+ after adding 5.0 mL of titrant are

Substituting these concentrations into the Nernst equation along with the formal
potential for the Fe3+/Fe2+ half-reaction, we find that the potential is:

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Dr. Mohamed E. I. Badawy Analytical Chemistry

At the equivalence point, the moles of Fe2+ initially present and the moles of Ce4+
added are equal. Because the equilibrium constant is large, the concentrations of Fe2+
and Ce4+ are exceedingly small and difficult to calculate without resorting to a
complex equilibrium problem. Consequently, we cannot calculate the potential at the
equivalence point, Eeq, using just the Nernst equation for the analyte’s half-reaction or
the titrant’s half-reaction. We can, however, calculate Eeq by combining the two
Nernst equations. To do so we recognize that the potentials for the two half-reactions
are the same; thus,

Adding together these two Nernst equations leaves us with

At the equivalence point, the titration reaction’s stoichiometry requires that

[Fe2+] = [Ce4+]
[Fe3+] = [Ce3+]
The ratio in the log term of the previous equation, therefore, equals one and the log
term is zero and then

After the equivalence point, the concentrations of Ce3+ and excess Ce4+ are easy to
calculate. The potential, therefore, is best calculated using the Nernst equation for the
titrant’s half-reaction.

For example, after adding 60.0 mL of titrant, the concentrations of Ce3+ and Ce4+ are

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Dr. Mohamed E. I. Badawy Analytical Chemistry

Substituting these concentrations into Nernst equation gives the potential.

Additional results for this titration curve are shown in the following Figure.

Selecting and Evaluating the End Point:

The equivalence point of a redox titration occurs when stoichiometrically
equivalent amounts of analyte and titrant react. As with other titrations, any difference
between the equivalence point and the end point is a determinate source of error.
Where Is the Equivalence Point?
In discussing acid–base titrations, we noted that the equivalence point is almost
identical with the inflection point located in the sharply rising part of the titration
curve.
If you look back at Figures in acid–base curves, you will see that the inflection
point is also in the middle of the titration curve’s sharp rise (we call this a
symmetrical equivalence point). This makes it relatively easy to find the equivalence

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Dr. Mohamed E. I. Badawy Analytical Chemistry

point when you sketch this titration curves. When the stoichiometry of a redox
titration is symmetrical (one mole analyte per mole of titrant), then the equivalence
point also is symmetrical. If the stoichiometry is not symmetrical, then the
equivalence point will lie closer to the top or bottom of the titration curve’s sharp rise.
In this case the equivalence point is said to be asymmetrical.
Finding the End Point with a Visual Indicator:
Three types of visual indicators are used to signal the end point in a redox
titration. A few titrants, such as MnO4–, have oxidized and reduced forms whose
colors in solution are significantly different. Solutions of MnO4– are intensely purple.
In acidic solutions, however, permanganate’s reduced form, Mn2+, is nearly colorless.
When MnO4– is used as an oxidizing titrant, the solution remains colorless until the
first drop of excess MnO4– is added. The first permanent tinge of purple signals the
end point.
A few substances indicate the presence of a specific oxidized or reduced species.
Starch, for example, forms a dark blue complex with I3– and can be used to signal the
presence of excess I3– (color change: colorless to blue), or the completion of a
reaction in which I3– is consumed (color change: blue to colorless). Another example
of a specific indicator is thiocyanate, which forms a soluble red-colored complex,
Fe(SCN)2+, with Fe3+.
The most important class of redox indicators, however, are substances that do not
participate in the redox titration, but whose oxidized and reduced forms differ in
color. When added to a solution containing the analyte, the indicator imparts a color
that depends on the solution’s electrochemical potential. Since the indicator changes
color in response to the electrochemical potential, and not to the presence or absence
of a specific species, these compounds are called general.
Iodometry:
Is a method of volumetric chemical analysis, a titration where the appearance or
disappearance of elementary iodine indicates the end point.
Usual reagents are sodium thiosulfate as titrant, starch as an indicator (it forms blue
complex with iodine molecules - though polyvinyl alcohol has started to be used
recently as well), and an iodine compound (iodide or iodate, depending on the desired
reaction with the sample).
The principal reaction is the reduction of iodine to iodide by thiosulfate:
I2 + 2 S2O32− → S4O62− + 2 I−

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Dr. Mohamed E. I. Badawy Analytical Chemistry

A common and illustrative use of iodometry is the measurement of concentration

of chlorine in water. Chlorine in pH under 8 oxidizes iodide to iodine. An
overabundance of potassium iodide is added to the known amount of sample in acidic
environment (pH < 4, the reaction is not complete in more alkaline pH). Starch is
added, forming blue clathrate complex with the liberated iodine. The blue solution is
then titrated with thiosulfate until the blue color vanishes.
Two possible sources of error can influence the outcome of the iodometric
titration. One is the air oxidation of acid-iodide solution and the other is the volatility
of I2. The first one can be eliminated by adding an excess of sodium carbonate in the
reaction vessel. This removes oxygen in the vessel by forming carbon dioxide(which
is heavier than air). The other error can be reduced by using an excess of iodide
solution which captures liberated iodine to form triiodide ions, I3−.
What is the difference between iodometry and iodimetry?
When an analyte that is a reducing agent is titrated directly with a standard iodine
solution, the method is called "iodimetry". When an analyte that is an oxidizing agent
is added to excess iodide to produce iodine, and the iodine produced is determined by
titration with sodium thiosulfate, the method is called "iodometry".
Redox indicators:
The relationship between a redox indicator’s change in color and the solution’s
electrochemical potential is easily derived by considering the half-reaction for the
indicator
Inox + ne– → Inred
Where Inox and Inred are, respectively, the indicator’s oxidized and reduced forms. The
Nernst equation for this reaction is:

If we assume that the indicator’s color in solution changes from that of Inox to that of
Inred when the ratio [Inred]/[Inox] changes from 0.1 to 10, then the end point occurs
when the solution’s electrochemical potential is within the range

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Dr. Mohamed E. I. Badawy Analytical Chemistry

Finding the End Point Potentiometrically:

Another method for locating the end point of a redox titration is to use an
appropriate electrode to monitor the change in electrochemical potential as titrant is
added to a solution of analyte.
The end point can then be found from a visual inspection of the titration curve.
The simplest experimental design consists of a Pt indicator electrode whose potential
is governed by the analyte’s or titrant’s redox half-reaction, and a reference electrode
that has a fixed potential.